HETEROCYCLES
An International Journal for Reviews and Communications in Heterocyclic ChemistryWeb Edition ISSN: 1881-0942
Published online by The Japan Institute of Heterocyclic Chemistry
Regular Issue
Vol. 22, No. 6, 1984
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■ Thermal Ring Expansion of 2-Vinylthiacycloalkane N-Imides by [2,3]-Sigmatropic Rearrangement
Haruki Sashida and Takashi Tsuchiya*
*School of Pharmacy, Hokuriku University, 3-Ho, Kanagawa machi, Kanazawa 920-1181, Japan
Abstract
The thermolysis of the 2-vinylthiacyclo-pentane, -hexane, and -heptane N-(p-toluenesulfonyl)imides (7) resulted in the [2,3]-sigmatropic rearrangement to give the corresponding ring expansion products (8).
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■ Crystal Structure Determination of the 2,6-Diphenyl-1,3,6,2-dioxazaphosphocane-p-monoborane Adduct. Evidence for the Lack of Transannular Interaction and Observation of a PhosphorusIV Atom Deformation towards Pseudopentacoordination
Rosalinda Contreras,* Apolonia Murillo, and Alain Klaébé
*Centro de Investigación y de Estudios Avanzados, Departmento de Química , I.P.N, Apartado 14-740, México, D.F., 07000, Mexico
Abstract
The X-ray crystal structure of the title compound shows a crown conformation of the ring and a strong 1,3 diaxial interaction between the P-BH3 group and the two corresponding hydrogens. This interaction leads an approach between the phosphorus and nitrogen. As a result the structure of phosphorusIV changes towards a pseudopentacoordinated geometry. The intracyclic Lewis interaction between N and P atoms is discarded due to the observed planarity of intracyclic anilic nitrogen.
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■ A Convenient Synthetic Method of 1-Acyl-2-aryl-3,3-dimethylindole Involving Isolable Diastereomeric Atropisomers
Takeo Kitamura,* Toshitaka Koga, Tanezo Taguchi, and Kazunobu Harano
*Daiichi College of Pharmaceutical Sciences, 22-1 Tamagawa-cho, Minami-ku, Fukuoka 815-0037
Abstract
The synthesis of 1-acyl-2-aryl-3,3-dimethylindoline was improved by the reaction of 1-acyl-2-hydroxy-3,3-dimethylindoline with an arene in the presence of BF3·O(C2H5)2 in dioxane, and stable diastereomeric atropisomers were isolated as products when the arene was β-naphthol.
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■ Reaction of α-Silyl Carbanion with Oxime Ethers
Takeo Konakahara,* Masayuki Matsuki, and Kenji Sato
*Department of Industrial Chemistry, Faculty of Science and Technology, Science University of Tokyo, 2641 Yamazaki, Noda, Chiba 278-8510, Japan
Abstract
In the presence of LDA, 2-(trimethylsilylmethyl)pyridine reacts with p-substituted benzaldoxime methyl ethers to give stereoselectively trans-2-aryl-3-(2-pyridyl)aziridines and (Z)-1-amino-1-aryl-2-(2-pyridyl)ethenes. From the temperature-dependent 1H-nmr spectra of trans-2-phenyl-3-(2-pyridyl)aziridine, ΔF* was estimated to be about 14 kcal / mol at the coalescence temperature (Tc = 0 °C).
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■ Mass Spectra of Hexahydroproaporphine Type Alkaloids
Sheng-Teh Lu* and Ian-Lih Tsai
*School of Pharmacy, Kaohsiung Medical College, 100 Shih Chuen 1st Rd., Kaohsiung 80708, Taiwan, R.O.C.
Abstract
Mass spectra of litsericine (1), N-methyllitsericine (2), lauformine (3) and N-methyllauformine (4) belonging to the hexahydroproaporphine group were measured, and the main fragmentation pathways for these alkaloids were presumed from the examination of their mass shifts.
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■ On the Configuration of the C5-Substituents of Lycopodium Alkaloids, 8-Deoxyserratinidine, Epidihydrofawcettidine, Serratinidine, and Dihydrofawcettidine
Takashi Harayama,* Tooru Taga, Kenji Oskai, and Kaoru Kuriyama
*Faculty of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan
Abstract
The configuration of the C5-substituents of 8-deoxyserratinidine, epidihydrofawcettidine, serratinidine, and dihydrofawcettidine was determined as formulas 2, 3, 4, and 5, respectively, by 1H-NMR, Brewster’s benzoate rule, and an X-ray analysis of 8-deoxyserratinidine.
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■ Reductive Formation of Pyrimidinylmethylenephosphoranes by Reaction of Trichloromethylpyrimidines with Triphenylphosphine
Shoetsu Konno, Yumi Sato, Takao Sakamoto, Nobuya Katagiri, and Hiroshi Yamanaka*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
The reaction of trichloromethylpyrimidines (1) with ca. 5 equivalent amounts of TPP gave pyrimidinylmethylenephosphoranes (9), whereas in the presence of 2 equivalent amounts of TPP, 1 was converted into the corresponding pyrimidinylchloromethylenephosphosphoranes (2). Condensation of 2 and 9 with aldehydes gave smoothly pyrimidine derivatives having an olefinic side chain. The pathway of the reduction to form the phosphoranes was discussed with experimental evidence.
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■ Reactions of 3-Dicyanomethyl-1-ethylbenzotriazolium Ylide with Acetylenic Esters
Enrique Díez-Barra, José Elguero, and Carmen Pardo*
*Departamento de Química Orgánica, Facultad de Química, Universidad Complutense de Madridas, Ciudad Universitaria, E-28040 Madrid, Spain
Abstract
The titled compound (1) reacts with acetylenic esters (2) giving 1:1 adducts (4), via 1,3-dipolar cycloaddition. Concerning the regioselectivity of the reaction, experimental results are in agreement with theoretical calculations and correspond to an inverted polarization of the azomethineimine moiety with regard to most known examples.
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■ Unexpected ’One-pot’ Formation of the Novel Macrocycle 1,8,15-Trithia[2.2.2](3,5)-1,3,4-thiadiazolinophane-4,11,18-trithione
Sebastiano Pappalardo,* Francesco Bottino, amd Corrado Tringali
*Dipartimento di Scienze Chimiche, Università di Catania, Viale A. Doria 8, I-95125 Catania, Italy
Abstract
The titie compound (1) is obtained in 15% yield from the reaction of equimolar amounts of 2,5-dimercapto-1,3,4-thiadiazole (2), dibromomethane and potassium hydraxide in ethanol. A possible mechanism, involvmg the self-condensation of the extremely reactive intermediate 3-bromomethyl-5-mercapto-1,3,4-thiadiazoline-2-thione (12a) to macrocycle (1), is proposed.
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■ Biotransformation of a Tetrahydroprotoberberine N-Metho Salt to a Spirobenzyisoquinoline Accompanying N-Methyl Group Transfer to O-Methyl Group by Callus Cultures of Corydalis Species
Kinuko Iwasa,* Akiko Tomii, Narao Takao, Toshimasa Ishida, and Masatoshi Inoue
*Kobe Pharmaceutical University, Motoyamakita, Higashinada, Kobe 658-8558, Japan
Abstract
The Structure and stereochemistry of base C, a 13-hydroxytetrahydroprotoberberine metabolite in cell cultures, have been determined by X-ray analysis. Thereby the biotransformation of a tetrahydroprotoberberine N-metho salt to a spirobenzylisoquinoline , involving a migration of the N-methyl group to the O-methyl group was first demonstrated.
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■ Synthesis of Indole and Related Compounds from Halo-nitroaromatics
Takao Sakamoto, Yoshinori Kondo, and Hiroshi Yamanaka*
*Pharmaceutical Institute, Pharmaceutical Institute, Aobayama, Sendai 980-8578, Japan
Abstract
5,7-Dimethyl-6-azaindole was synthesized by treatment of 3-amino-2,6-dimethyl-4-pyridineacetaldehyde diethyl acetal with hydrochloric acid in boiling ethanol. According to the similar manner, indole and ethyl 4-indolecarboxylate were obtained from the corresponding 2-aminophenylacetaldehyde derivatives in satisfactory yields. The starting materials were easily prepared by palladium-catalyzed cross-coupling reaction of o-halonitroaromatics with trimethylsilylacetylene followed by the reaction with sodium ethoxide and catalytic reduction of the o-nitro group.
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■ Claisen Rearrangement of Meta-substituted Aryl Propargyl Ethers in Poly(ehtylene glycol)
Usha Rao and Kalpattu Kuppuswami Balasubramanian*
*Department of Chemistry, Indian Institute of Technology, Madras, 600 036, India
Abstract
The thermal rearrangement of meta-substituted aryl propargyl ethers was studied in poly(ethylene glycol)-200. The rearrangement was not regiospecific.
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■ A New Preparation of an Ochotensin-type Isoquinoline by Photolysis
Yoshiro Hirai, Hiroyuki Egawa, and Takao Yamazaki*
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
The photolysis of 1-benzoyl-3,4-dihydroisoquinoline hydrochlorides (3) and (4) gave spirobenzylisoquinolines (5) and (6).
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■ The Influence of Alkyl Substituents on Internal Photodimerization of Pyrimidine-6-azapyrimidine Dinucleotide Analogues
Jadwiga Jankowska, Henryk Koroniak, and Krzysztof Golankiewicz*
*Facluty of Chemistry, Adam Mickiewicz University, ul. Grunwaldzka 6, 60-780 Poznán, Poland
Abstract
The new internal photodimers of dinucleotide analogues in which 5-alkyl derivatives of uracil and 6-azauracil are connected with trimethylene chain have been obtained. The structure is discussed on the basis of spectroscopic data.
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■ Addition of Phthalimido Nitrene to Substituted Cyclopentadienes
Krishna Narasimhan* and Perumal Raja Kumar
*Department of Organic Chemistry, Guindy Campus, University of Madras, Chennai-600 025, India
Abstract
The aziridines 3,3a and 3b obtained by the cycloaddition of phthalimidonitrene to cyclopentadiene derivatives 2, 2a and 2b undergoes facile ring expansion, when treated with sodium hydride to give substituted pyridine derivatives 4, 4a and 4b respectively. Hydrazinolysis of the aziridines gives the cyclopentadiene derivatives through the intermediacy of N-aminoaziridines 5,5a and 5b. Oxidation of the aziridines 3,3a with lead tetraacetate gives ths aziridine 6 and 6a.
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■ A Novel Photochemical Method for the Synthesis of Flavonols
T. Sudhakar Rao, Anil Kumar Singh, and Girish Kumar Trivedi*
*Department of Chemistry, Indian Institute of Technology, Powai, Bombay 400 076, India
Abstract
Photolysis of the nitrochromenes followed by acidic hydrolysis of the photoproducts yields the corresponding flavonols in high yields.
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■ 2-Aryl-oxazolo- and Thiazolopyridines. Synthesis via Cyclization of N-(2-Chloro-3-pyridinyl)arylamides and Thioamides
Axel Couture* and Pierre Grandclaudon
*Laboratoire de Chimie Organique Physique, Université des Sciences et Technologies de Lille, 59655 Villeneuve d’ Ascq Cedex, France
Abstract
Chloropyridinylenamides can be easily converted into oxazalo- and thiazolo [5,4-b]pyridines by treatment with polyphosphoric acid and Lawesson reagent respectively.
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■ Epoxidation of 3-(3’-Butenyl)-4-hydroxycoumarins and Intramolecular 6-Exo Cyclization to 3,4-Dihydro-2-hydroxymethyl-2H,5H-pyrano[2,3-b][1]benzopyran-5-one
Pierfrancesco Bravo,* Giuseppe Resnati, Calimero Ticozzi, and Giancarlo Cavicchio
*CNR, Centro Studio Sostanze Organiche Naturali, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano, Italy
Abstract
Several 3-(3’-butenyl)-4-hydroxycoumarins were synthetized and oxidized with m-chloroperbenzoic acid. 3,4-Dihydro-2-hydroxymethyl-2H,5H-pyranol[2,3-b][1]benzopyran-5-ones were obtained through an intramolecular 6-Exo cyclization of intermediate epoxide.
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■ A Convenient Synthesis of Novel 3-Amidino-2-oxo-1,2-dihydroquinoxaline
Yoshihisa Kurasawa,* Yoshihisa Okamoto, and Atsushi Takada
*School of Pharmaceutical Sciences, Kitasato University, Shirokane, Minato-ku, Tokyo 108-8641, Japan
Abstract
The reactions of 3-(5-oxo-1,2,4-oxadiazolin-3-yl)-2-oxo-1,2-dihydroquinoxaline (2) and 2-oxo-1,2-dihydroquinoxaline-3-amidoxime (3), derived from 3-cyano-2-oxo-1,2-dihydroquinoxaline (1), with FeSO4-HCl and Fe-HCl afforded Fe(II) complexes of 3-amidino-2-oxo-1,2-dihydroquinoxaline (4), whose treatment with NaOH gave the free ligand 4.
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■ Syntheses and Reactions of Pyridazine Derivatives XX. Studies on the Radical Methylation of the 1,2-Diazine System
Gottfried Heinisch* and Gerhard Lötsch
*Institut für Pharmazeutische Chemie, Universität Wien , Pharmaziezentrum, Althanstrasse, 14 A-1090 Wien, Austria
Abstract
Protonated pyridazines (1,2,3) on reaction with methyl radical (generated by oxidative decarboxylation of acetic acid or by redox reaction of t-BuOOH/FeSO4·7H2O) are shown mainly to be attacked at positions β to the nitrogen atoms. However, formation of compounds 2,4,5,6,8,9 and 10 indicates lower degree of regioselectivity compared with homolytic benzylation or acylation of the 1,2-diazine system. Synthesis of ethyl 5-styryl-4-pyridazinecarboxylates (13,14) was achieved by homolytic methylation of ethyl 4-pyridazinecarboxylate (11) followed by condensation with aromatic carbaldehydes.
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■ Synthesis of Novel Carboxyl Porphyrins and Their Iron Complexes: 5,10,15,20-Tetra[α,α,α,α-o-(2,2-dimethyl-ω-carboxylalkanamido)phenyl]porphinato Iron Complexes
Yoh-ichi Matsushita, Etsuo Hasegawa, Kiyoshi Eshima, and Eishun Tsuchida*
*School of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan
Abstract
Novel porphyrin derivatives having 2,2-dimethyl-ω-carboxylalkyl chains as amphiphilic moieties and their iron complexes are synthesized. The typical compound is bromo-5,10,15,20-tetra[α,α,α,α-O-(2,2-dimethyl-12-carboxyldodecanamido)phenyl]porphinato iron(III). The lipophilic-liophilic balance can be controlled by changing the alkyl chain length.
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■ A Stereoselective Synthesis of 1,5-Disubstituted Thieno[3’,2’:3,4]piperidino[1,2-c]oxazolidin-3-ones through N-Oxaacyliminium Ion Cyclization
Shinzo Kano,* Yoko Yuasa, Tsutomu Yokomatsu, and Shiroshi Shibuya
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
A stereoselective synthesis of 1-phenyl- (5) and 5-methyl-1-phenylthieno[3’,2’:3,4]piperidino[1,2-c]oxazolidin-3-ones (8a,b) was achieved by reduction of the corresponding N-substituted 5-phenyloxazolidine-2,4-diones (4, 7a,b) with diisobutylaluminum hydride, followed by treatment of the reduction products with formic acid. Reduction of 8a,b with LiAlH4 afforded the corresponding 4-(α-hydroxybenzyl)-6-methylthieno[3,2-c]pyridines (10a,b), respectively.
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■ Consecutive Menschutkin Reaction of Cyclic Amines with Dichloromethane under High Pressure: Synthesis of Methylenebisamines
Kiyoshi Matsumoto,* Shiro Hashimoto, Yukio Ikemi, and Shinichi Otani
*Graduate School of Human and Environmental Studies, Kyoto University, Yoshida-Nihonmatsu-cho, Sakyo-ku, Kyoto 606-8501, Japan
Abstract
The reaction of heterocyclic amines such as pyrrolidine, piperidines, and morpholines with dichloromethane in methanol in the kiro bar region affording the corresponding methylenebisamines is described.